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UNIVERSITY  OF  ILLINOIS 


_ , ' Max„.g5i9il., 

-2; 

X 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 


Louis...  Arnold. ..Slfigriat 

ENTITLED .Tho...Re.s.o.lu.ti.Qn  .o.f...Amino..  .Ac.i.dj3...T.lar.Q.ui5)a....the 

.C.  gwp.p.d.Q.r . . . .Su  .1  .f.  p.n.ara.i  da.  s.  .* 

IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF L.a.Q.dalo.r...oi...S.c.lfcn.ce 


O 

Instructor  in  Charge 


Approved  ; 


HEAD  OF  DEPARTMENT  OF 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/resolutionofaminOOsieg 


Table  of  Contents 


Page 

Acknowledgment  1 

I.  Introduction  2 

II.  Theoretical  and  Historical  Discussion  4 

III.  Experimental  6 

Preparation  of 

(a)  Phenyl  amino  acetic  acid  6 

(b ) Camphor  sulfonic  acid  7 

(c)  Camphor  sulfonyl  chloride  7 

(d)  Camphor  sulfonamide  of  7 

dl-phenyl  anino  acetic  acid 

(e)  Analysis  of  caiiphor  sulfonamide  8 

of  dl-phenyl  amino  acetic  acid 

(f)  Rotation  of  camphor  sulfonamide  9 

of  dl-phenyl  anino  acetic  acid 

(g)  Preparation  of  camphor  sulfonamide  9 

of  aniline 

(h)  Rotation  ana  analysis  of  camphor  9 

sulfonamide  of  aniline 

(i)  Hydrolysis  of  casnphor  sulfonamide  10 

of  aniline 

(j  ) Pre-paration  of  camphor  sulfonaimide  10 

of  p-toluidine 

(k)  Rotation  and  analysis  of  camphor  10 

sulfonamide  of  p-toluidine 

(l)  Camphor  sulfonamide  of  secondary  11 

butyl  amine 


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Resolution  of  dl-phenyl  amino 

12 

acetic  acid 

(n) 

Sujaaraary 

14 

(o) 

Bibliography 

16 

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ACKliOvrLEDGIvOtlJT 

The  writer  desiree  to  express  his  sincere  thanks 
and  appreciation  to  Dr*  C*S,  Marvel  for  his  helpful 
suggestions  and  guidance  during  the  course  of  this 
investigation . 


2 


THE  RESOLUTION  OF  AMINO  ACIDS  THROUGH  THE  CAJ/iPHOR  SULFCNAl-HDES . 

I.  INTRODUCTION 

Pure,  optically  active  aroino  acids  are  of  importance  in 
the  study  and  investigation  of  the  protein  minimum.  The 
natural  amino  acids,  however,  differ  from  the  synthetic  acids 
in  that  the  former  are  optically  active,  v/hereas  the  latter 
are  inactive.  Consequently,  a short  method  of  resolving  amino 
acids  is  desirable . 

The  method  of  resolving  amino  acids  now  in  general  use, 
is  the  so-called  Fischer  method.  The  amino  group  is  first 
covered  with  some  radical,  such  as  the  formyl  or  benzoyl 
radical.  An  active  alEaloid  salt  of  the  amido  acid  is  then 
prepared  and  submitted  to  fractional  crystallization.  The 
d-and  1-  forms  of  the  amino  acid  are  then  regenerated  by  de- 
composing the  salt  and  hydrolysing  off  the  protective  group 
above  mentioned. 

The  present  work  was  undertaken  v^ith  the  hope  of  finding 
a shorter  method  of  resolving  amino  acids.  It  was  thought 
that  if  the  amino  group  was  covered  with  an  acid  radical 
containing  an  asymmetric  carbon-atom,  Fischer's  method  could 
be  shortened  by  two  steps.  Cati'jphor  sulfonyl  chloride  when 
condensed  with  an  amino  acid  should  yield  a sulfonamide,  easily 
crystallizable  from  suitable  solvents.  Phenyl  amino  acetic 
acid  was  used  because  it  is  easily  and  cheaply  prepared.  Also, 
since  the  rotations  of  the  d-snd  1-acids  are  known,  it  was 


easy  to  check  up  the  accuracy  of  this  method.  A condensation 
as  above  mentioned  should  yield,  in  the  case  of  phenyl  aroino 


r'  • . '‘yy^''^i%^,  . vc^  't  r.  ._  ’ ■''^r^CTlfe'if  *}  • *;.'' 


. 4«n|&*|fe|f^^i5.«A'}:.  .i^si ' sht:^  | i- 


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1 


acetic  acid: 

d-camphor  sulfonamide  of  1-pdenyl  amino  acetic 
d-camphor  sulfonamide  of  d-phenyl  amino  a.cetic 
wnich  should  be  easily  separated  by  fractional 


acid 

acid 

crystallization. 


f 


4 


II.  THEORETICAL  AND  HISTORICAL  DISCUSSION. 

The  phenyl  amino  acetic  acid  was  prepa.red  according  to 
the  method  of  Zelinsky  and  Stadinoff^,  as  modified  by  Marvel 

and  Noyes  . No  increase  in  the  yield  was  obtained  by  substitut- 
ing benzene  for  methyl  alcohol  as  the  solvent  for  the  benzalde- 
hyde  in  the  preparation  of  the  amino  cyanide.  However,  by 
employing  a mechanical  stirrer,  the  time  was  cut  from  three 
days  to  about  three  hours.  The  yield  varied  between  30  and 

D1  phenyl  airjino  acetic  acid  has  been  resolved  by  two 

3 

different  methods.  Fischer  effected  the  resolution  by  cover- 
ing the  amine  group  with  the  formyl  raaical  and  then  preparing 
the  quinine  salt  for  crystallization.  Betti  and  Mayer"^ 
effected  the  resolution  by  preparing  the  camphor  sulfonic 
acid  salt  of  the  amino  acid. 

We  attempted  to  resolve  the  dl  acid  through  the  camphor 
sulfonamide.  Equimolecular  portions  of  dl-phenyl  amino  acetic 
acid,  cajophor  sulfonyl  chloride  and  sodium  hydroxide  were 

O 

stirred,  at  0,  until  everything  dissolved  and  then  the  amide 

was  precipitated  v/ith  hydrochloric  acid.  The  camphor  sulfonic 

acid  and  camphor  sulfonyl  chloride  were  prepared  according 

to  the  method  of  Reychler'".  His  yields  were  duplicated  in 
all  cases. 

Attempts  to  prepare  the  camphor  sulfonamide  of  the  amino 
acid  by  a condensation  in  inert  solvents,  such  as  dry  ether 
and  dry  benzene  were  without  success.  Even  after  refluxing  a 
mixture  of  amino  acid  and  camphor  sulfonyl  chloride  twenty 
four  hours,  no  trace  of  the  amide  could  be  found.  This  is 


>k'',i,l-‘-^'  "'  ;■■'  i ■'  5o  ' ' .'^  ■,  '‘j-  " U 'W' 


■v-'‘  V ..;  'r{.  obwwvi^^'jb'.i-::'  Virjbb^’ 

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' '•'  $ii>l«i5  ' l>5ifiQrj  n sb  y J!>t-'  •’ 

*^-'  ' ■>  . ■ ' Vv,'-\'V  W' V 

‘ • '; ' ' \ ^ : : :’®‘  ?'":; 

[*  '"^'  • '■  " ■"''  ' ■'  ''  i‘  ■ . ■ ‘V  ■ ^ ' -''  “ ■’  "'i  ^■’‘^.•■'^  ■ 

i ' ’^oi  to  »i/^ 

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b 

further  evidence  of  the  theory  tha.t  amino  acids  form  inner 
ring  salts. 


0 


H-K-H 


H 

In  this  type  of  compound  the  nitrogen  is  pentavalent,  and 
the  hydrogens  on  the  nitrogen  are  unreactive. 

In  order  to  study  the  physical  constants,  rotations, 
and  ease  of  hydrolysis  of  various  camphor  sulfonamides,  we 
prepared  the  amide  of  aniline,  p-toluidine , and  secondary 
"butyl  amine.  They  were  prepared  by  condensing  the  amino  acid 
(2  parts)  with  camphor  sulfonyl  chloride  (Ipart)  in  dry  benzene. 
The  amide  was  obtained  from  the  benzene  solution. 

It  was  found  that  the  camphor  sulfonamide  of  aniline  and 
p-toluidine  could  be  readily  hydrolysed  with  48^^  hydrobromic 
acid.  An  attempt  to  hydrolyse  the  amide  of  d-phenyl  amino 
acetic  acid  was  Vi/ithout  success,  perhaps  because  of  the  small 
quantities  of  material  at  hand  and  the  lack  of  time. 

The  resolution  of  camphor  sulfonamide  of  dl-phenyl  amino 
acetic  acid  was  effected  in  '70%  alcohol.  The  d-amide  separ- 


J 


ates  out  first 


r.  f-j  • , * ^ . . > . . . .'.  >5;  ■•.*•  » . 'a 


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6 


LI  I . EXP3  HIMENT  AL . 

Phenyl  Amino  Acetic  Acid.  The  method  used  was  that  of 
Zelinsky  and  Stadinoff^  as  modified  hy  Marvel  and  Koyes^. 

One  hundred  ten  gms.  of  sodium  cyanide  were  dissolved  in 
200  cc.  of  water  and  114  gms.  of  ammonium  chloride  were  added. 

To  this  was  added,  with  stirring,  a solution  of  212  gms.  of 
henzaldehyde  in  200  cc.  of  methyl  alcohol,  and  the  mixture 
was  stirred  for  about  five  hours.  The  mixture  becomes  quite 
warm  at  first,  cooling  down,  however,  in  the  course  of  the 
reaction.  After  five  hours  the  stirring  was  stopped  and  one 
liter  of  water  was  added  which  threw  out  the  oily  amino  cyanide. 
This  was  collected  in  1 liter  of  benzene  and  washed  with  water. 
The  aminocyanide  was  extracted  from  the  benzene  by  shaking  tv/ice 
with  oOO  cc.  of  hydrochloric  acid  (3  parts  acid  to  1 part  water). 
The  acid  solution  was  refluxed  about  fpur  hours,  in  order  to 
hydrolyse  the  amino  cyanide,  cooled,  filtered  from  some  tarry 
material,  and  the  free  an'jino  acid  precipita.ted  with  ammonium 
hydroxide.  The  amino  acid  was  filtered  off  with  suction,  and 
washed  with  water  and  alcohol  to  remove  color.  The  yield 
varied  from  120  to  130  gms,  (40-43^  of  the  calculated  amount). 

The  following  method  did  not  increase  the  yield  of  amino 
acid.  One  hundred  ten  gms,  of  sodium  cyanide  and  114  gms.  of 
powdered  ammoniuni  chloride  were  placed  in  a.  flask  and  212  gms. 
of  benzaldehyde  dissolved  in  500  cc,  of  benzene  was  added. 

Ten  cc.  of  water  was  added  to  the  mixture,  and  the  flask  was 
shaken  vigorously.  The  reaction  mixture  was  allowed  to  stand 
three  days,  being  shaken  occasionally.  After  three  days,  some 


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7 


insoluble  material  was  filtered  off,  the  benzene  shalcen  v/ith 
hydrochloric  acid  ( 1:2.  by  volume  ) and  the  acid  layer  reflux- 
ed abput  two  hours.  After  cooling  the  mixture,  the  free  amino 
acid  was  precipitated  Vi^ith  ammonium  hydroxide.  The  yield  was 
120  gms.  or  41^  of  theory.  Longer  hydrolysis  did  not  improve 
the  yiela  in  either  of  the  two  methods  above  outlined. 

The  amino  acid  as  purified  by  washing  with  alcohol  still 
retains  some  color.  An  attempt  to  purify  the  acid  further  by 
boneblacking  an  alkaline  solution,  resulted  in  a decided  loss 
of  product.  The  best  method  of  purification  is  recrystalliza- 
tion from  hot  water  using  a little  boneblack. 

Camphor  Sulfonic  Acid.--  The  camphor  sulfonic  acid  was 
prepared  according  to  the  method  of  Reychler^,  duplicating 
his  yields  in  all  instances.  In  one  instance,  redistilled 
acetic  anhydride  was  used,  and  from  227  gms.  of  cai^iphor  a 
yield  of  127  gms.  or  55^^  of  the  sulfonic  acid  v/as  obtained, 
althoutiii  the  average  yields  Vi/ere  between  of  theory.  These 

yields  are  based  on  the  amount  of  camphor  actually  used.  By 
pouring  the  filtrate,  from  the  crystallized  camphor  sulfonic 
acid,  into  about  three  liters  of  cold  water,  v/e  were  able  to 
recover  from  70-80  gms.  of  camphor  from  each  run. 

Camphor  Sulfon vl  Chloride The  camphor  sulfonyl  chloride 
was  prepared  according  to  the  method  of  Reychler^.  The  average 
yields  were  between  50-65^  of  the  calculated  amount,  although 
in  one  case  71^  v/as  obtained. 

Camphor  Sulfonamide  of  Dl- phenyl  Amino  Acetic  Acid. --Place 


12.5  gms.  of  dl-phenyl  amino  acetic  acid  in  a flask  and  add 


J 

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8 


3.4  gms.  of  sodium  hydroxide  in  100  cc.  of  water.  Stir  and 
cool  to  0^.  Now  add  25  , camphor  sulfonyl  chloride,  and 

during  two  hours,  add  gradually  3.4  gms.  of  sodium  hydroxide 
in  100  cc.  water,  keeping  the  mixture  well  agitated.  After 
all  the  sodium  hydroxide  is  added,  continue  the  stirring  for 
two  hours,  then  filter  and  precipitate  the  camphor  sulfonamide 
v.ith  hydrochloric  acid.  Filter  the  amide  and  recrystallize  from 
dilute  alcohol  (50^).  The  yields  varied  between  13-15  gms. 
or  40-50^  of  the  theoretical  amount.  The  pure  amide  is  a 
white  crystalline  product  melting  at  165-70°. 

An  attempt  was  made  to  condense  the  amino  acid  writh 
canjphor  sulfonyl  chloride  in  dry  benzene  and  dry  ether  but 
the  results  were  negative.  The  sodium  salt  of  dl-phenyl  amino 
acetic  acid  was  prepared  and  refluxed  with  camphor  sulfonyl 
chloride  in  dry  ether,  but  no  amide  was  obtained. 

The  rotation  on  the  camphor  sulfonamide  of  dl-phenyl 
amino  acetic  acid  as  freshly  prepared  varies  with  the  number 
of  crystallizations  probably  on  account  of  the  difference  in 
solubility  of  the  two  isomers  present.  Analysis  of  the 
camphor  sulfonamide  of  phenyl  amino  acetic  acid  for  nitrogen 


(Kjeldahl)  gave  the  following  results 

I II 

weitiht  of  sample  0.15  g.  0.15  g. 

cc.  HCl  used  (N.F.  0.1998)  10.2  10.2 

ca:.  NaOH  used  (N.F,  0.1115)  14.0  13.7 

% nitrogen  found  3.6^ 

% nitrogen  calculated  3.8/^  3.8^ 


1 


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0.4000  gms.  of  substarice  dissolved  ir  12.2645  gms.  of  95^ 


Camphor  Sulfonamide  of  Aniline Five  gms.  of  aniline 
and  7 gms.  of  campdor  sulfonyl  chloride  were  placed  in  a 
small  flask  and  covered  with  50  cc.  of  dry  benzene.  This 
mixture  was  allov/ed  to  stand  over  night  or  for  several  days 
(if  more  convenient),  with  occasional  shaking.  The  solution 
was  filtered  from  the  aniline  hydrochloride  formed,  and  the 
benzene  distilled  off.  The  oily  residue  was  taken  up  in 
hot  dilute  alcohol  (50^)  and  allowed  to  crystallize.  Upon 
recrystallization  from  50^  alcohol,  the  amide  melts  at 
117 .5-118. 5*^  (corrected) . The  rotation  in  95^  alcohol 
was  determined.  0.8616  gras,  of  substance  dissolved  in 

o 

12.1206  gms.  of  95^  alcohol  gave  a rotation  off-1.65  in  a 
1 dcm.  tube  for  the  sodium  line,  or  . 

Analysis  of  the  amide  for  nitrogen  (K.jeldahl)  gave  the 
following  results 


alcohol  gave  a rotation  offO.S^*  in  a 1 dcm.  tube  for  the 


sodium  line,  or  C°<Jjj=fil,4 


0 


weight  of  sample 
cc.  HCl.  used  (K.F,  0.1998J 
cc.  KaOH  used  (K.F.  0.1115) 
% nitrogen  found 
% nitrogen  calculated 


10.0 


13.6 


0.15g 


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10 


Hydrolysis  o.f  the  Caiuphor  Sulf  onairjide  of  An  Hire. 

Three  gms.  of  the  ajDide  v.?ere  refluxed  for  about  two 
hours  v.'ith  48^  hydrobronic  acid.  After  cooling  the  solu- 
tion was  made  alkaline  and  extracted  v/ith  ether,  and  the 

ether  evaporated.  The  oily  residue  had  the  odor  of  aniline, 

0 

The  benzene  sulfonyl  chloride  derivative  melted  at  95-100. 
Correct  melting  point  110°, 

Camphor  Sulfonamide  p_f  P-toluidine :--  Five  gms.  of  p- 

toluidine  end  5,7  gras,  of  camphor  sulfonyl  chloride  were 

mixed  in  a small  flask  end  covered  with  50cc,  dry  benzene. 

This  reaction  mixture  was  v;orked  up  in  a manner  similar  to 

the  one  described  in  the  previous  experiment.  The  pure 

amide  melts  at  137-138  (corrected), 

0,2148  gms.  of  substaiice  dissolved  in  12.2333  gms,  of 

0 

95^0  alcohol  gave  a.  rotation  of  +0.32  in  a 1 dem,  tube  for 

the  sodium  line,  or  R 7-  +23.2  , 

D 

Analysis  of  the  aiwiae  for  nitrogen  (K.1eldahl)  gave 
the  following  results :-- 


weight  of  sample 

0 . 30g 

cc.  HGl.  used  (II. F.  0.1998) 

10.4 

cc.  NaOH.  used  (K.F.  0.1115) 

10.6 

% nitrogen  found 

4.1^ 

^ nitrogen  calculated 

4.3^ 

The  hydrolysis  of  a 1 gra . sample  of  amide  v;as  carried 
out  in  the  same  manner  as  described  in  the  previous  experi- 
ment. This  amide  was  also  readily  hydrolysed. 


•V  ' /’  . ••'  -.f  . ',; 

i • it i : : i ; .•:  •'  . 

I ■ , ■ . 

-.  ...••:’  \.’i  i jj|f.7.x.t<  r 


1>_  :C'ti  ,'^9' 


I ^ 


. : nr  ;>  Vocj-j  iX;, 

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'/,■•.•'»' y*- 

•V' 

' '■  ^ ' ' y*',  . , ■ 


..t 

t rf  ^ ' 

i 

r ^ 

* ‘ 


11 


Camphor  Sulfonamide  of  Secondary  Butyl  Amine;--  Three  gms. 
of  secondary  "butyl  amine  and  b.3  i^s.  of  camphor  sulfonyl 
chloride  v/ere  placed  in  a small  flask  and  covered  with  30  cc. 
dry  "benzene.  The  secondary  butyl  amine  hydrochloride  formed, 
being  quite  valuable,  was  filtered  off  and  saved.  The  oil 
left  after  evaporation  of  the  benzene  was  taken  up  in  hot  50^ 
alcohol,  and  allowed  to  cool.  But  it  was  only  after  standing 
in  a refrigerator  for  several  hours  that  crystals,  mixed 
v/ith  an  oily  product  appeared.  The  crystals  were  white  needles, 
A second  crop  of  crystals  was  obtained  by  placing  the  alcoholic 
solution  of  the  oil  in  a.  refrigerator  for  another  twenty  four 
hours.  Since  secondary  butyl  amine  contains  an  asymmetric 
carbon-atom,  it  was  thought  that  we  could  thus  obtain  the 
optical  isomers  of  the  amide.  But  due  to  the  low  melting 
point  of  the  amide  this  v/as  not  further  investigated.  No 
rotation  was  .axen  on  the  amide  and  no  analysis  v/as  made.  The 
first  crop  of  crystals  melted  40-46  (uncorrected}. 


[■.V’  , ...  ].^-^  i 

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12 


Resolution  of  Dl-Pinenyl  Airano  Acetic  Acid 
Solubility  of  Carfluiior  Sulfonainide  of  Dl«Phenvl  Amino 
Acetic  Acid  in  Alcoholj--  Five  gms.  of  the  amide  were 
dissolved  in  100  cc.  of  hot  alcohol  (s.g.  0.88)  and  allow- 
ed to  stand  for  24  hours.  1.64  gms.  of  the  amide  separated 
out  during  this  period.  This  crop  of  crystals  had  a specific 

O 

rotation  of-t8.8  . After  another  24  hours,  a second  crop 
of  crystals  (1.01  gms.)  separated  out,  and  these  possessed 

a specific  rotation  of  only  +5.4°.  In  order  to  check  the 
above  solubility,  if  possible,  an  excess  of  the  amide  was 
allov/ed  to  stand  in  contact  with  lOcc.  of  70^  alcohol  (cold). 
After  three  days  the  undissolved  amide  was  filtered  off  and 
the  filtrate  carefully  evaporated.  This  yielded  0.1593  gms* 
of  dry  amide.  Hence  lOOcc.  of  cold  70^c  alcohol  will  dissolve 
approximately  1.6  gms.  of  the  camphor  sulfonamide. 

Fractional  Crystallization  o f the  Camphor  Sulfonamide 
of  Dl-Phenyl  Airino^Ace  iic  Acids  i--  Fifteen  gms.  of  camphor 
sulfonamide  of  dl-phenyl  amino  acetic  acid  v/ere  dissolved 
in  100  cc.  hot  70?"^  alcohol.  After  24  hours,  11  gms.  of  amide 
were  filtered  off.  0.3980  gms.  dissolved  in  12.2190  gras. 

O 

9b%  alcohol  gave  a rotation  of-tO.56  in  a 1 dcrn . tube  for 

0 

the  sodium  line,  or  [c< +13.8  . The  filtrate  was  concec- 

trated  one  third  its  voluTne  and  after  24  hours  2 gms.  of  amide 

were  filtered  off.  0.3850  gms.  of  substance  dissolved  in 

0 

12.3480  gras.  95^  alcohol  gave  a rotation  of  -0.05  in  a 
1 dcm.  tube  for  the  sodium  line,  or  [°<]^-  -1.9  . 


13 


The  second  filtrate  was  again  concentrated  one  third 
its  volume  and  after  24  hours,  1 gm.  of  ainide  was  filtered 
off.  0.3080  gras,  of  substance  dis  :;olved  in  12.S210  gms.  of 
9dfo  alcohol  gave  a rotation  of  -0.24  in  a 1 . dcm.  tube  for 


the  sodium  line,  or[c(J~  -11.3  • 


T|tt,>.  ^ tlH'^'  / ry~Ij':^  ' '.‘■vfV^'^i^-i'*.  »'-.  -'  a -I  V;.'x  V''*V?»^'i5VV' 


-iV:' ^ ■^" 

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P^i  . 


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14 


SUIMARY 

1.  A shorter  method  of  preparing  dl-phenyl  amino 
acetic  acid  was  worked  out. 

2.  The  method  of  Reychler  for  preparing  camphor  sulfon- 
ic acid  and  aamphor  sulfonyl  chloride  were  studied  and  his 
yields  duplicated. 

3.  The  camphor  sulfonamides  of  various  primary  amines 
were  prepared  and  studied.  They  could  be  readily  hydrolysed 
with  hydrobromic  acid, 

4.  The  camphor  sulfonamide  of  dl-phenyl  amino  acetic 
acid  could  not  be  prepared  by  condensing  the  amino  acid  with 
camphor  sulfonyl  chloride  in  an  inert  solvent, 

5.  The  dextro  and  laevo  rotatory  amides  of  phenyl  amino 
acetic  acid  were  prepared  but  the  free  acids  could  not  be 
isolated, 

6.  In  the  course  of  this  investigation  the  follov/ing  new 
compounds  were  prepared 

(a)  d-camphor  sulfonamide  of  aniline. 

(b ) d-camphor  sulfonaaide  of  p-toluidine, 

(c)  d-ca;;phor  sulfonamide  of  secondary  butyl  amine. 

(d)  d-caraphor  sulfonamide  of  dl-phenyl  amino  acetic  acid. 


r 


c: 


'i  ^ 


>-.r  W.a>4WPTMi^ -i--4 

“ii. 


\. 


* * *‘. 
■ i-  , 


.vvj  .r  ,,  . 


r*  «r^7^-frC' 


V ■.:,»; 


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15 


Camphor  Sulfon- 

M.P. 

Specific 

Analysis 

Calcu- 

amide  of 

Rot at i on 

for  Nitro-  lated 
gen  found 

(a)  secondary 
butyl  amine 

40-44° 

— 



(b ) aniline 

117.5  -- 
18.5" 

t28.8° 

4.4f/^ 

4, 5 fa 

(c )p-toluidine 

137-8° 

+23. 2" 

4,1  fa 

4,3fo 

(d)  dl-phenyl  amino 
acetic  acid 

165-70° 

+11.4° 

z.efa 

ffiSSMB,  '% , i.'icr  ■ ',%■ 

. ■•  H’  - ^ jt-^ i m 


w '• ' ‘ “sS  .«■  ”,  ^,'1'^  If  >.  iXi  - ‘V^:i'yi''  ■ iis.fi J\iii!^;^i):  jy,. 

■,.  


iii  '."* 


'.V.'  ,*  ' • -J  - 


^ i.  -' 

. ■?* 


y* 


t 

U - * * "•  • • V?c  'ii'  -'•  ’■•  ;■’  ' * ‘«->r  ■:■ 

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ji 


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16 


BIBLIOGRi>J>HY 


1.  Zelinsky  and  Stadinoff, 

2.  Marvel  and  Noyes, 

3.  Fischer  and  Meichland, 

4.  Betti  and  Mayer, 

5.  Reychler, 


Ber.,  39,  1725  (1906). 

J.  Amer.  Chem,  8oc.,  42, 
2264  (1920). 

Ber.,  41,  1287  (1908). 
Ber.,  41,  2072  (1908). 
Bull.  Soc.  Ohem,,  (3)  19, 
120-128  (1898). 


